US11805699B2 - Compositions and methods for doped thermoelectric ceramic oxides - Google Patents
Compositions and methods for doped thermoelectric ceramic oxides Download PDFInfo
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- US11805699B2 US11805699B2 US17/060,537 US202017060537A US11805699B2 US 11805699 B2 US11805699 B2 US 11805699B2 US 202017060537 A US202017060537 A US 202017060537A US 11805699 B2 US11805699 B2 US 11805699B2
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- thermoelectric ceramic
- metal dopant
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Definitions
- the disclosure in one aspect, relates to doped thermoelectric ceramic oxide compositions comprising a calcium cobaltite ceramic.
- the disclosed doped thermoelectric ceramic oxide compositions have an increased energy conversion efficiency as compared to an undoped or conventional thermoelectric ceramic oxide materials.
- methods for making the doped thermoelectric ceramic oxide compositions are also disclosed herein.
- products and devices comprising the thermoelectric ceramic oxide compositions, e.g., solid-state conversion devices that can utilize heat to generate electricity.
- thermoelectric ceramic oxide having the following formula: Ca 3-x M 2 x Co 4 O 9 M 1 y ; wherein x is a number having a value from about 0.00 to about 3; wherein y is a number having a value from about 0.01 to about 0.50; wherein M 1 is a first metal dopant comprises a metal selected from group 1 metals, group 2 metals, transtition metals, post-transitional metals, group 14 metals, group 15 metals, group 16 metals, and rare earth elements; and wherein M 2 is a second metal dopant comprising at least one rare earth element.
- Also disclosed herein are methods of making a doped thermoelectric ceramic oxide comprising: doping a ceramic oxide formulation with a first metal dopant, M 1 , in a sol-gel process resulting in a gel; heating the gel to form an ash; grinding the ash into an ash-based powder; compressing the ash-based powder into a pellet; and sintering the pellet to form the doped thermoelectric ceramic oxide.
- thermoelectric ceramic oxide composition Also disclosed herein are solid-states conversion device comprising a disclosed thermoelectric ceramic oxide composition.
- thermoelectric ceramic oxide composition made by a disclosed method of making same.
- FIG. 1 shows a representative schematic illustrating an exemplary procedure for fabrication of polycrystalline ceramics pellets with the precursor powders made from the conventional chemical sol-gel route.
- FIGS. 2 A- 2 F shows representative data illustrating temperature dependence of: ( FIG. 2 A ) electrical resistivity (p-T), ( FIG. 2 B ) Seebeck coefficient (S-T), and ( FIG. 2 C ) electrical power factor (S 2 /p-T); and ( FIG. 2 D ) total thermal conductivity (K-T), ( FIG. 2 E ) electronic contribution (K e ) and lattice contribution (K i ), and ( FIG. 2 F ) thermoelectric figure of merit (ZT) for Ca 3-x Tb x Co 4 O 9 Bi y .
- FIGS. 3 A- 3 B representative characteristic XRD peaks from Ca 3 Co 4 O 9 phase with monoclinic symmetry were identified for Ca 2.95 Tb 0.05 Co 4 O 9 Bi y samples.
- FIG. 3 B shows (003) diffraction peak showing the shift to a lower Bragg's angle. Line corresponds to position of peak in the undoped Ca 3 Co 4 O 9 .
- FIGS. 4 A- 4 G show representative SEM images of Ca 3-x Tb x Co 4 O 9+ ⁇ Bi y samples after sintering stage.
- Cross-sectional SEM images of Ca 3-x Tb x Co 4 O 9+ ⁇ Bi y samples from the fractured surface are as follows: ( FIG. 4 A ) Ca 3 Co 4 O 9+ ⁇ , ( FIG. 4 B ) Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ , ( FIG. 4 C ) Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ Bi 0.10 , ( FIG. 4 D ) Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ Bi 0.15 , ( FIG. 4 E ) Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ Bi 0.20 , ( FIG. 4 F ) Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ Bi 0.25 , and ( FIG. 4 G ) Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ Bi 0.30 .
- FIGS. 5 A- 5 I show representativew TEM and STEM images showing the nanostructure of the Ca 3-x Tb x Co 4 O 9 Bi y samples showing atomic structure of the grain boundaries is further revealed by the atomic resolution Z-contrast imaging.
- FIGS. 5 A, 5 D, and 5 G show Z contrast from the samples with unary single dopant Tb;
- FIGS. 5 B, 5 E, and 5 H show Z contrast from the samples with unary single dopant Bi;
- FIGS. 5 C, 5 F, and 5 I show Z contrast from the samples with dual dopants.
- FIGS. 5 A- 5 I show representativew TEM and STEM images showing the nanostructure of the Ca 3-x Tb x Co 4 O 9 Bi y samples showing atomic structure of the grain boundaries is further revealed by the atomic resolution Z-contrast imaging.
- FIGS. 5 A, 5 D, and 5 G show Z contrast from the samples with unary single dopant Tb
- FIGS. 5 B, 5 E, and 5 H show Z contrast from
- FIG. 5 A, 5 B, and 5 C show the nanostructure of the lattice and grain boundary for Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ , Ca 3 Co 4 O 9+ ⁇ Bi 0.25 , and Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ Bi 0.25 , respectively.
- the arrows show the position of Tb in the rock salt layer CaO inside the lattice.
- black arrows show the position of Bi in the rock salt layer CaO inside the lattice
- the′ white arrows show the position of Bi in the rock salt layer CoO in both the lattice and the grain boundary.
- FIG. 5 G shows a grain boundary free of secondary phase with dopant inclusion.
- black arrows show the position of dopants in the rock salt layer CaO in both the lattice and the grain boundary
- the white arrows show the position of the dopants in the rock salt layer CoO in both the lattice and the grain boundary.
- FIG. 6 A- 6 C show schematic drawings showing the dual dopant dopants has resulted in the systematic microstructure evolution, where: FIG. 6 A is Ca 3 Co 4 O 9+ ⁇ ; FIG. 6 B is Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ ; and FIG. 6 C is Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ Bi 0.25 .
- FIGS. 7 A- 7 E show representative data illustrating temperature dependence of thermoelectric properties for different state-of-the-art p-type materials, including: ( FIG. 7 A ) p-T, ( FIG. 7 B )S-T, ( FIG. 7 C ) S 2 /p-T, ( FIG. 7 D ) K-T, and ( FIG. 7 E ) ZT.
- FIGS. 8 A- 8 F shows representative data illustrating temperature dependence of Ca 3-x Tb x Co 4 O 9 samples: ( FIG. 8 A ) electrical resistivity (p-T), ( FIG. 8 B ) Seebeck coefficient (S-T), and ( FIG. 8 C ) electrical power factor (S 2 /p-T); and ( FIG. 8 D ) total thermal conductivity (K-T), ( FIG. 8 E ) electronic contribution (K e ) and lattice contribution (K i ), and ( FIG. 8 F ) thermoelectric figure of merit (ZT).
- SEM images of plan-view surfaces are as follows: ( FIG. 9 A ) Ca 3 Co 4 O 9+ ⁇ ; ( FIG. 9 B ) Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ ; ( FIG. 9 C ) Ca 2.71 Tb 0.3 Co 4 O 9+ ⁇ ; and ( FIG. 9 D ) Ca 2.5 Tb 0.5 Co 4 O 9+ ⁇ .
- Cross-sectional SEM images from the fractured surface are as follows: ( FIG. 9 E ) Ca 3 Co 4 O 9+ ⁇ ; ( FIG. 9 F ) Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ ; ( FIG. 9 G ) Ca 2.71 Tb 0.3 Co 4 O 9+ ⁇ ; and ( FIG. 9 H ) Ca 2.5 Tb 0.5 Co 4 O 9+ ⁇ .
- FIGS. 10 A- 10 F shows TEM images showing the nanostructure of the Ca 2.95 Tb 0.05 Co 4 O 9 Bi y samples.
- FIGS. 10 A and 10 B show the grain boundary from the crystals with different c-axis orientations for Ca 2.95 Tb 0.05 Co 4 O 9+ ⁇ .
- the black circles on the TEM in FIG. 10 A images indicate the electron beam sample areas for the EDS data acquisition indicated on FIG. 10 B .
- the circles on the TEM FIG. 10 D images indicate the electron beam sample areas for the EDS data acquisition indicated on FIG. 10 E .
- FIGS. 10 C and 10 F show EDS data obtained on the grain boundaries and grain interior as shown in FIGS. 10 B and 10 F , respectively.
- FIG. 11 shows a representative timeline of the improvement in the ZT of Ca 3 Co 4 O 9+ ⁇ polycrystalline materials by the addition of different doping elements.
- *ZT value of representative disclosed Examples is shown; it is believed that a ZT material over 1 is possible for the disclosed materials.
- FIGS. 12 A- 12 B show STEM images showing the nanostructure of the Ca 2.95 Tb 0.05 Co 4 O 9 Bi 0.25 for a simulation.
- FIG. 12 A shows the simulated STEM image of the nanostructure of the Ca 2.95 Tb 0.05 Co 4 O 9 Bi 0.25 .
- FIG. 12 B shows the representation of the associated 3D crystal structure used in the simulation.
- ratios, concentrations, amounts, and other numerical data can be expressed herein in a range format. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as “about” that particular value in addition to the value itself. For example, if the value “10” is disclosed, then “about 10” is also disclosed. Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms a further aspect. For example, if the value “about 10” is disclosed, then “10” is also disclosed.
- a further aspect includes from the one particular value and/or to the other particular value.
- ranges excluding either or both of those included limits are also included in the disclosure, e.g. the phrase “x to y” includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’ and less than ‘y’.
- the range can also be expressed as an upper limit, e.g. ‘about x, y, z, or less’ and should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘less than x’, less than y′, and ‘less than z’.
- the phrase ‘about x, y, z, or greater’ should be interpreted to include the specific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as the ranges of ‘greater than x’, greater than y′, and ‘greater than z’.
- the phrase “about ‘x’ to ‘y’”, where ‘x’ and ‘y’ are numerical values, includes “about ‘x’ to about ‘y’”.
- a numerical range of “about 0.1% to 5%” should be interpreted to include not only the explicitly recited values of about 0.1% to about 5%, but also include individual values (e.g., about 1%, about 2%, about 3%, and about 4%) and the sub-ranges (e.g., about 0.5% to about 1.1%; about 5% to about 2.4%; about 0.5% to about 3.2%, and about 0.5% to about 4.4%, and other possible sub-ranges) within the indicated range.
- the terms “about,” “approximate,” “at or about,” and “substantially” mean that the amount or value in question can be the exact value or a value that provides equivalent results, or effects as recited in the claims or taught herein. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and/or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art such that equivalent results or effects are obtained. In some circumstances, the value that provides equivalent results or effects cannot be reasonably determined.
- the term “effective amount” refers to an amount that is sufficient to achieve the desired modification of a physical property of the composition or material
- the terms “optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.
- temperatures referred to herein are based on atmospheric pressure (i.e. one atmosphere).
- thermoelectric (TE) power generators (Ref. 84, 85) or devices that possess the ability to directly transform temperature gradients into electrical power.
- TE devices have no moving parts, are silent, and provide a relatively maintenance-free operation.
- TE devices could enable a wide range of applications from solid state cooling to high temperature power generations and have potential to dramatically improve the total efficiency of energy utilization, and to suppress the consumption of fossil fuels. (Refs. 86, 87, 88).
- Thermoelectric (TE) technology could be more efficient if the high-performance thermoelectric materials were made of non-toxic and earth-abundant elements.
- the energy conversion efficiency of TE materials is characterized by the dimensionless figure-of-merit, (Ref. 4) ZT.
- S is the Seebeck coefficient
- a is the electrical conductivity
- S 2 ⁇ is the electrical power factor
- K is the thermal conductivity
- T is the absolute temperature.
- TE materials include conventional p-type TE materials available commercially such as bismuth antimony telluride (Bi 0.5 Sb 1.5 Te 3 ) and silicon germanium (Si 80 Ge 20 ) which hold ZT values of about 1. Even though the performance of those materials is spectacular, they are usually heavy, toxic, and low in abundance as natural resources, and their thermal or chemical stability are generally inferior. (Refs. 9, 10) Moreover, particularly for those of SiGe (Ref. 9) and Yb 14 MnSb 11 (Ref. 10) that have superior stability, they only function in the strict oxygen-free environment at high temperatures.
- ceramic oxide materials offer significant advantages due to their lower cost, lighter weight, non-toxicity.
- ceramic oxide materials are more suitable for high temperature applications because of their structural and chemical stability in air.
- oxide ceramics are traditionally regarded as poor TE materials because their carrier concentrations and mobility are two or three orders of magnitude lower than that conventional TE materials, and lead to low electrical conductivities.
- thermoelectric ceramic oxide composition comprising a doped calcium cobaltite ceramic can provide dramatically increased thermoelectric conversion efficiency as compared to the undoped ceramic.
- using a systematic doping comprising a non-stoichiometric addition of Bismuth (Bi) in Ca 3 Co 4 O 9 ceramics can result in ceramic materials can achieve a ZT that surpasses that of undoped pristine Ca 3 Co 4 O 9+ ⁇ ceramics.
- the resulting ceramic materials can achieve a ZT that surpasses that of undoped pristine Ca 3 Co 4 O 9+ ⁇ ceramics as well as that of the single crystal.
- the dual-doped polycrystalline cobaltite oxide with designed novel non-stoichiometry Ca 2.95 Tb 0.05 Co 4 O 9 Bi y reached the peak ZT of 0.9, which is ⁇ 260% increase to that of the undoped pristine Ca 3 Co 4 O 9+ ⁇ ceramics and outperforming single crystal.
- Such performance enhancement is achieved by concurrent intragranular doping and intergranular dopants grain boundary segregation that lead to large increase ( ⁇ 460% at low temperature; ⁇ 230% at high temperature) of electrical power factor.
- the present disclosure sheds light about the new direction for engineering the grain boundaries to dramatically improve the performance of various TE materials.
- thermoelectric ceramic oxide compositions comprising a doped calcium cobaltite ceramic Ca 3 Co 4 O 9+ ⁇ .
- the disclosed doped thermoelectric ceramic oxide composition can have dramatically increased thermoelectric conversion efficiency as compared to the undoped calcium cobaltite ceramic.
- the disclosed doped calcium cobaltite ceramic results in the presence of the dopant in both intergranular and intragranular structures.
- thermoelectric ceramic oxide compositions comprising a doped thermoelectric ceramic oxide having the following formula: Ca 3-x M 2 x Co 4 O 9 M 1 y ; wherein x is a number having a value from about 0.00 to about 3; wherein y is a number having a value from about 0.01 to about 0.50; wherein M 1 is a first metal dopant comprises a metal selected from group 1 metals, group 2 metals, transtition metals, post-transitional metals, group 14 metals, group 15 metals, group 16 metals, and rare earth elements; and wherein M 2 is a second metal dopant comprising at least one rare earth element.
- the disclosed thermoelectric ceramic oxide compositions comprise a grain boundary wherein at least a portion of the first metal dopant and/or the second metal dopant are at or proximal to the grain boundary.
- segregation of at least a portion of the first metal dopant and/or the second metal dopant to or proximal to the grain boundary improves the performance of the disclosed thermoelectric ceramic oxide compositions, e.g., Seeback coefficient, compared to conventional prior art thermoelectric ceramic oxide compositions.
- thermoelectric ceramic oxide compositions wherein at least one dopant, e.g., at least a portion of the first metal dopant and/or the second metal dopant, are at or proximal to the grain boundary should be generally applicable to a variety of thermoelectric materials, including, but not limited to, the present disclosed thermoelectric ceramic oxide compositions.
- thermoelectric ceramic oxide compositions can be optimized and tuned via the manipulation of type and amount of dopants present at the grain boundary. That is, manipulation and optimization of the composition and density of intra-grain doping and inter-grain (interfacial) precipitation at the grain boundary provides the ability to finely tune structure-property optimization for thermoelectric materials generally, as well as other materials.
- a dopant system for the thermoelectric ceramic oxide comprises a first dopant.
- the dopant system comprises a non-stoichiometric addition of a first dopant.
- the first metal dopant may be selected from group 14, group 15, or group 16 metals, or a rare earth element.
- the first metal dopant is a metal selected from Potassium (K), Bismuth (Bi), Cerium (Ce), Niobium (Nb), Ytterbium (Yb), Lutetium (Lu), or Barium (Ba).
- the first metal dopant is Bi.
- the first metal dopant is provided as a non-stoichiometric addition to the calcium cobaltite ceramic.
- the doped ceramic material has a formula Ca 3 Co 4 O 9+ ⁇ M 1 y , where M 1 represents the first dopant, as described herein, and y is a number having a value from about 0.01 to about 0.50, or from about 0.10 to about 0.40, or from about 0.15 to about 0.30, or from about 0.20 to about 0.25. In certain aspects, y can have a value of about 0.05 or about 0.10 or about 0.15 or about 0.20 or about 0.25 or about 0.30 or about 0.35 or about 0.40, or about 0.45 or about 0.50.
- the disclosed thermoelectric ceramic oxide comprises a dual dopant system comprising a first metal dopant and one or more second dopants.
- the one or more second dopants of the dual dopant system are provided as a substitution for a portion of the calcium component in the calcium cobaltite.
- each of the one or more second dopants is a metal selected from the rare earth elements.
- each of the one or more second dopants is a metal selected from Lanthanum (La), Cerium (Ce), Praseodymium (Pr), Neodymium (Nd), Promethium (Pm), Samarium (Sm), Europium (Eu), Gadolinium (Gd), Terbium (Tb), Dysprosium (Dy), Holmium (Ho), Erbium (Er), Thulium (Tm), Ytterbium (Yb), Lutetium (Lu)
- the first metal dopant is Terbium.
- the one or more second metal dopant comprises Tb.
- the one or more second dopants are provided in an amount to provide a stoichiometric substitution for a portion of the calcium in the ceramic.
- the undoped ceramic has the formula Ca 3 Co 4 O 9+ ⁇
- the disclosed doped ceramic oxide would have a formula in which the one or more second dopants would be provided in an amount “x”, and the Ca in the ceramic oxide would be reduced by the same number x to (3-x).
- x is a number having a value of from about 0.0 to about 0.10, or from about 0.01 to about 0.09, or from about 0.02 to about 0.08, or from about 0.03 to about 0.07, or from about 0.04 to about 0.06.
- x can have a value of about 0.01 or about 0.02 or about 0.03 or about 0.04 or about 0.05 or about 0.06 or about 0.07 or about 0.08 or about 0.09 or about 0.10.
- the disclosed doped thermoelectric ceramic oxide has a formula Ca 3-x M 2 x Co 4 O 9 M 1 y , where M′ represents a first dopant, as describe herein, M 2 represents the one or more second dopants, as described herein, x is a number having a value of from about 0.00 to about 0.10, and y is a number having a value of from about 0.01 to about 0.50.
- the disclosed doped thermoelectric ceramic oxide has a formula Ca 3-x Tb x Co 4 O 9 Bi y , where x is a number having a value of from about 0.00 to about 0.10, or any range or set of intermediate values encompassed by the foregoing range, and y is a number having a value of from about 0.01 to about 0.50, or any range or set of intermediate values encompassed by the foregoing range.
- the optimized value for y may be unique to each unique value of x.
- the doped thermoelectric ceramic oxide comprises a first metal dopant or a second metal dopant in the intragranular structures, the intergranular structures, or both.
- the first dopant, the second dopant, or both are present in the intragranular structures.
- the first dopant, the second dopant, or both can substitute for one or more Ca or Co in the Ca 3 Co 4 O 9 lattice, such as in the CaO layer or in the CoO layer.
- the disclosed doped thermoelectric ceramic oxide compositions have at least one grain boundary between adjacent grains.
- the at least one grain boundary may be discrete or continuous, or a combination thereof.
- the first metal dopant is present at one or more of the grain boundaries.
- the disclosed doped thermoelectric ceramic oxide compositions are characterized by a significant increase in the electrical conductivity and Seebeck coefficient.
- the disclosed dual dopant system results in systematic microstructure evolution, including the increased grain anisotropy, improved crystal grain alignment and the segregation of dopants at the grain boundaries.
- the disclosed doped thermoelectric ceramic oxide compositions have a ZT value of at least about 0.40, about 0.41, about 0.42, about 0.43, about 0.44, about 0.45, about 0.46, about 0.47, about 0.48, about 0.49, about 0.50, about 0.51, about 0.52, about 0.53, about 0.54, about 0.55, about 0.56, about 0.57, about 0.58, about 0.59, about 0.60, about 0.61, about 0.62, about 0.63, about 0.64, about 0.65, about 0.66, about 0.67, about 0.68, about 0.69, about 0.70, about 0.71, about 0.72, about 0.73, about 0.74, about 0.75, about 0.76, about 0.77, about 0.78, about 0.79, about 0.80, about 0.81, about 0.82, about 0.83, about 0.84, about 0.85, about 0.86, about 0.87, about 0.88, about 0.89, about 0.90, about 0.91, about 0.92, about 0.93, about 0.94, about 0.95, about 0.96, about 0.97,
- a disclosed Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a ZT value of at least about 0.40, about 0.41, about 0.42, about 0.43, about 0.44, about 0.45, about 0.46, about 0.47, about 0.48, about 0.49, about 0.50, about 0.51, about 0.52, about 0.53, about 0.54, about 0.55, about 0.56, about 0.57, about 0.58, about 0.59, about 0.60, about 0.61, about 0.62, about 0.63, about 0.64, about 0.65, about 0.66, about 0.67, about 0.68, about 0.69, about 0.70, about 0.71, about 0.72, about 0.73, about 0.74, about 0.75, about 0.76, about 0.77, about 0.78, about 0.79, about 0.80, about 0.81, about 0.82, about 0.83, about 0.84, about 0.85, about 0.86, about 0.87, about 0.88, about 0.89, about 0.90, about 0.91, about 0.92, about 0.93, about 0.94, about 0.95
- the disclosed doped thermoelectric ceramic oxide compositions have a ZT value that is greater than a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by at least about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17% about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27% about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37% about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47% about 48%, about 49%, about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57% about 58%, about 59%, about 60%, about 61%,
- a disclosed Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a ZT value greater than an undoped Ca 3 Co 4 O 9 oxide ceramic material by at least about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17% about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27% about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37% about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47% about 48%, about 49%, about 50%, about 51%, about 52%, about 53%, about 54%, about 55%, about 56%, about 57% about 58%, about 59%, about 60%, about 61%, about 62%, about 63%, about 64%, about
- the disclosed doped thermoelectric ceramic oxide compositions have a ZT value that is greater than a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by about 10% to about 300%. In a further aspect, the disclosed doped thermoelectric ceramic oxide compositions have a ZT value that is greater than a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by about 50% to about 300%.
- the disclosed doped thermoelectric ceramic oxide compositions have a ZT value that is greater than a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by about 100% to about 300%. In a yet further aspect, the disclosed doped thermoelectric ceramic oxide compositions have a ZT value that is greater than a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by about 150% to about 300%.
- the disclosed doped thermoelectric ceramic oxide compositions have a ZT value that is greater than a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by about 10% to about 200%. In a further aspect, the disclosed doped thermoelectric ceramic oxide compositions have a ZT value that is greater than a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by about 50% to about 200%.
- the disclosed doped thermoelectric ceramic oxide compositions have a ZT value that is greater than a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by about 100% to about 200%. In a yet further aspect, the disclosed doped thermoelectric ceramic oxide compositions have a ZT value that is greater than a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by about 150% to about 200%.
- a disclosed Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a ZT value greater than an undoped Ca 3 Co 4 O 9 oxide ceramic material by about 10% to about 300%.
- adisclosed Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a ZT value greater than an undoped Ca 3 Co 4 O 9 oxide ceramic material by about 50% to about 300%.
- a disclosed Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a ZT value greater than an undoped Ca 3 Co 4 O 9 oxide ceramic material by about t 150% to about 300%.
- a disclosed Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a ZT value greater than an undoped Ca 3 Co 4 O 9 oxide ceramic material by about 10% to about 200%.
- a disclosed Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a ZT value greater than an undoped Ca 3 Co 4 O 9 oxide ceramic material by about 50% to about 200%.
- a disclosed Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a ZT value greater than an undoped Ca 3 Co 4 O 9 oxide ceramic material by about 100% to about 200%.
- a disclosed Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a ZT value greater than an undoped Ca 3 Co 4 O 9 oxide ceramic material by about 150% to about 200%.
- the disclosed doped thermoelectric ceramic oxide compositions have a thermal conductivity that is decreased compared to a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by less than about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17% about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27% about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37% about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47% about 48%, about 49%, about 50%; or any combination of
- a disclosed Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a thermal conductivity that is decreased compared to an undoped Ca 3 Co 4 O 9 oxide ceramic material by less than about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17% about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27% about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37% about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47% about 48%, about 49%, about 50%; or any combination of the foregoing values; or a range having
- the disclosed doped thermoelectric ceramic oxide compositions have a thermal conductivity that is decreased compared to a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by less than about 1% to about 25%. In a further aspect, the disclosed doped thermoelectric ceramic oxide compositions have a thermal conductivity that is decreased compared to a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by less than about 5% to about 20%.
- the disclosed doped thermoelectric ceramic oxide compositions have a thermal conductivity that is decreased compared to a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by less than about 5% to about 10%.
- the disclosed doped thermoelectric ceramic oxide compositions have a thermal conductivity that is decreased compared to a undoped thermoelectric ceramic oxide composition consisting of essentially the same composition of ceramic oxide without a first or a second metal dopant by less than about 15% to about 20%.
- a disclosed Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a thermal conductivity that is decreased compared to an undoped Ca 3 Co 4 O 9 oxide ceramic material by less than about 1% to about 25%.
- the Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a thermal conductivity that is decreased compared to an undoped Ca 3 Co 4 O 9 oxide ceramic material by less than about 5% to about 20%.
- Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a thermal conductivity that is decreased compared to an undoped Ca 3 Co 4 O 9 oxide ceramic material by less than about 10% to about 20%.
- Ca 3-x M 2 x Co 4 O 9 M 1 y material would have a thermal conductivity that is decreased compared to an undoped Ca 3 Co 4 O 9 oxide ceramic material by less than about 15% to about 20%.
- the present disclosure pertains to methods of making a doped thermoelectric ceramic oxide comprising: doping a ceramic oxide formulation with a first metal dopant, M 1 , in a sol-gel process resulting in a gel; heating the gel to form an ash; grinding the ash into an ash-based powder; compressing the ash-based powder into a pellet; and sintering the pellet to form the doped thermoelectric ceramic oxide.
- the present disclosure relates to methods of making the doped thermoelectric ceramic oxide materials disclosed herein.
- a methods of making the disclosed doped thermoelectric ceramic oxide comprising the steps of: dissolving in water the following: citric acid, ethylene glycol, polyethylene glycol, nitric acid, a calcium nitrate salt, a cobalt nitrate salt, and a salt comprising a cation of the first metal dopant described herein; stirring the solution under heat to form a gel; converting the gel to ash by applying heat to the gel; grinding the ash; calcining the ground ash to form a powder; pressing the powder to form a pellet; and sintering the pellet to form a doped thermoelectric ceramic oxide.
- a method of making the disclosed doped thermoelectric ceramic oxide comprising the steps of: dissolving in water the following: citric acid, ethylene glycol, polyethylene glycol, nitric acid, a calcium nitrate salt, a cobalt nitrate salt, and a salt comprising a cation of Bi, Ce, Nb, Yb, Lu, or Ba; stirring the solution under heat to form a gel; converting the gel to ash by applying heat to the gel; grinding the ash; calcining the ground ash to form a powder; and pressing the powder to form a pellet; and sintering the pellet to form a doped thermoelectric ceramic oxide.
- a method of making the disclosed doped thermoelectric ceramic oxide comprising the steps of: dissolving in water the following: citric acid, ethylene glycol, polyethylene glycol, nitric acid, Ca(NO 3 ) 2 ⁇ 4H 2 O, Co(NO 3 ) 2 ⁇ 6H 2 O, and Bi(NO 3 ) 3 ⁇ 5H 2 O; stirring the solution under heat to form a gel; converting the gel to ash by applying heat to the gel; grinding the ash; calcining the ground ash to form a powder; and pressing the powder to form a pellet; and sintering the pellet to form a doped thermoelectric ceramic oxide.
- thermoelectric ceramic oxide in a further aspect, disclosed are methods of making a doped thermoelectric ceramic oxide comprising the steps of: doping a ceramic oxide formulation with a first metal dopant in a sol-gel process resulting in a gel; heating the gel to form an ash-based powder; compressing the ash-based powder into a pellet; and sintering the pellet to form the doped thermoelectric ceramic oxide having a grain boundary phase that comprises an oxide of the first dopant; wherein the doped thermoelectric ceramic oxide has the molecular formula Ca 3 Co 4 O 9+ ⁇ M 1 y , where M 1 represents the first dopant, and y is a number having a value from about 0.01 to about 0.50, or any range or set of intermediate values encompassed by the foregoing range.
- thermoelectric ceramic oxide in a further aspect, disclosed are methods of making a doped thermoelectric ceramic oxide comprising the steps of: doping a ceramic oxide formulation with a first metal dopant in a sol-gel process resulting in a gel; heating the gel to form an ash-based powder; compressing the ash-based powder into a pellet; and sintering the pellet to form the doped thermoelectric ceramic oxide having a grain boundary phase that comprises an oxide of the first dopant; wherein the doped thermoelectric ceramic oxide has the molecular formula Ca 3 Co 4 O 9+ ⁇ Bi y , where y is a number having a value from about 0.01 to about 0.50, or any range or set of intermediate values encompassed by the foregoing range.
- a method of making the disclosed doped thermoelectric ceramic oxide comprising the steps of: dissolving in water the following: citric acid, ethylene glycol, polyethylene glycol, nitric acid, a calcium nitrate salt, a cobalt nitrate salt, and a salt comprising a cation of Bi; stirring the solution under heat to form a gel; converting the gel to ash by applying heat to the gel; grinding the ash; calcining the ground ash to form a powder; and pressing the powder to form a pellet; and sintering the pellet to form a doped thermoelectric ceramic oxide.
- the present disclosure relates to methods for making the doped thermoelectric ceramic oxide materials disclosed herein.
- a methods of making the disclosed doped thermoelectric ceramic oxide comprising the steps of: dissolving in water the following: citric acid, ethylene glycol, polyethylene glycol, nitric acid, a calcium nitrate salt, a cobalt nitrate salt, a salt comprising a cation of the first metal dopant described herein, and a salt comprising a cation of the second metal dopant described herein; stirring the solution under heat to form a gel; converting the gel to ash by applying heat to the gel; grinding the ash; calcining the ground ash to form a powder; pressing the powder to form a pellet; and sintering the pellet to form a doped thermoelectric ceramic oxide.
- a method of making the disclosed doped thermoelectric ceramic oxide comprising the steps of: dissolving in water the following: citric acid, ethylene glycol, polyethylene glycol, nitric acid, a calcium nitrate salt, a cobalt nitrate salt, and a salt comprising a cation of Bi, Ce, Nb, Yb, Lu, or Ba, and a salt comprising a cation of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu; stirring the solution under heat to form a gel; converting the gel to ash by applying heat to the gel; grinding the ash; calcining the ground ash to form a powder; and pressing the powder to form a pellet; and sintering the pellet to form a doped thermoelectric ceramic oxide.
- a method of making the disclosed doped thermoelectric ceramic oxide comprising the steps of: dissolving in water the following: citric acid, ethylene glycol, polyethylene glycol, nitric acid, a calcium nitrate salt, a cobalt nitrate salt, and a salt comprising a cation of Bi, and a salt comprising a cation of Tb; stirring the solution under heat to form a gel; converting the gel to ash by applying heat to the gel; grinding the ash; calcining the ground ash to form a powder; and pressing the powder to form a pellet; and sintering the pellet to form a doped thermoelectric ceramic oxide.
- a method of making the disclosed doped thermoelectric ceramic oxide comprising the steps of: dissolving in water the following: citric acid, ethylene glycol, polyethylene glycol, nitric acid, Ca(NO 3 ) 2 ⁇ 4H 2 O, Co(NO 3 ) 2 ⁇ 6H 2 O, Bi(NO 3 ) 3 ⁇ 5H 2 O, and Tb(NO 3 ) 3 ⁇ 6H 2 O; stirring the solution under heat to form a gel; converting the gel to ash by applying heat to the gel; grinding the ash; calcining the ground ash to form a powder; and pressing the powder to form a pellet; and sintering the pellet to form a doped thermoelectric ceramic oxide.
- thermoelectric ceramic oxide in a further aspect, disclosed are methods of making a doped thermoelectric ceramic oxide comprising the steps of: doping a ceramic oxide formulation with a first metal dopant and a second metal dopant in a sol-gel process resulting in a gel; heating the gel to form an ash-based powder; compressing the ash-based powder into a pellet; and sintering the pellet to form the doped thermoelectric ceramic oxide having a grain boundary phase that comprises an oxide of the first dopant; wherein the doped thermoelectric ceramic oxide has the molecular formula Ca 3-x M 2 x Co 4 O 9 M 1 y where M 1 represents a first dopant, as describe herein, M 2 represents the one or more second dopants, as described herein, x is a number having a value of from about 0.00 to about 0.10, or any range or set of intermediate values encompassed by the foregoing range, and y is a number having a value of from about 0.01 to about 0.50, or any range or set of intermediate values
- thermoelectric ceramic oxide in a further aspect, disclosed are methods of making a doped thermoelectric ceramic oxide comprising the steps of: doping a ceramic oxide formulation with a first metal dopant and a second metal dopant in a sol-gel process resulting in a gel; heating the gel to form an ash-based powder; compressing the ash-based powder into a pellet; and sintering the pellet to form the doped thermoelectric ceramic oxide having a grain boundary phase that comprises an oxide of the first dopant; wherein the doped thermoelectric ceramic oxide has the molecular formula Ca 3-x Tb x Co 4 O 9 Bi y , where x is a number having a value of from about 0.00 to about 0.10, or any range or set of intermediate values encompassed by the foregoing range, and y is a number having a value of from about 0.01 to about 0.50, or any range or set of intermediate values encompassed by the foregoing range.
- the suitable temperature in the first step is a temperature from about 290 K to about 380 K. In a still further aspect, the suitable temperature in the first step is a temperature from about 291 K to about 379 K. In a yet further aspect the suitable temperature in the first step is a temperature from about 292 K to about 378 K. In a still further aspect, the suitable temperature in the first step is a temperature from about 293 K to about 377 K. In a yet further aspect, the suitable temperature in the first step is a temperature from about 294 K to about 376 K. In a still further aspect, the suitable temperature in the first step is a temperature from about 295 K to about 375 K.
- the suitable temperature in the first step is a temperature from about 296 K to about 374 K. In a still further aspect, the suitable temperature in the first step is a temperature from about 297 K to about 373 K. In a yet further aspect, the suitable temperature in the first step is a temperature from about 298 K to about 373 K.
- the suitable temperature in the first step is a temperature of about 290 K, about 295 K, about 300 K, about 305 K, about 310 K, about 315 K, about 320 K, about 325 K, about 330 K, about 335 K, about 340 K, about 345 K, about 350 K, about 355 K, about 360 K, about 365 K, about 370 K, about 375 K, a range encompassed by any of the foregoing values, any combination of the foregoing values, or any set of intermediate values encompassed by a range comprising the foregoing values.
- the suitable time in the first step is a time from about 10 min to about 24 h. In a further aspect, the suitable time in the first step is a time from about 1 h, about 2 h, about 3 h, about 4 h, about 5 h, about 6 h, about 7 h, about 8 h, about 9 h, about 10 h, about 11 h, about 12 h, about 13 h, about 14 h, about 15 h, about 16 h, about 17 h, about 18 h, about 19 h, about 20 h, about 21 h, about 22 h, about 23 h, about 24 h, a range encompassed by any of the foregoing values, any combination of the foregoing values, or any set of intermediate values encompassed by a range comprising the foregoing values.
- the disclosed methods of making a dope thermoelectric ceramic oxide comprises as a second step ashing of the gel formed in the first step carried out at a suitable temperature.
- ashing of the gel formed in the first step is carried out a temperature of about 630 K to about 930 K.
- ashing of the gel forme in the first step is carried out a temperature of about 630 K, about 640 K, about 650 K, about 660 K, about 670 K, about 680 K, about 690 K, about 700 K, about 710 K, about 720 K, about 730 K, about 740 K, about 750 K, about 760 K, about 770 K, about 780 K, about 790 K, about 800 K, about 810 K, about 820 K, about 830 K, about 840 K, about 850 K, about 860 K, about 870 K, about 880 K, about 890 K, about 900 K, about 910 K, about 920 K, about 930 K, a range encompassed by any of the foregoing values, any combination of the foregoing values, or any set of intermediate values encompassed by a range comprising the foregoing values.
- the disclosed methods of making a doped thermoelectric ceramic oxide comprises as a third step grinding the ashed material formed in the second step, thereby forming a ground material, and then calcining the ground material for an suitable period of time at a suitable temperature, thereby forming a precursor powder.
- grinding can be carried out by a suitable apparatus, such as a ball mill.
- the calcining can be carried out in a suitable apparatus, such as a furnace or tube furnace.
- the suitable temperature for calcining is about 873 K to about 1350 K, a range encompassed by any of the foregoing values, any combination of the foregoing values, or any set of intermediate values encompassed by a range comprising the foregoing values.
- the suitable period of time for calcining is a time from about 10 min to about 24 h.
- the suitable time in the third step is a time from about 1 h, about 2 h, about 3 h, about 4 h, about 5 h, about 6 h, about 7 h, about 8 h, about 9 h, about 10 h, about 11 h, about 12 h, about 13 h, about 14 h, about 15 h, about 16 h, about 17 h, about 18 h, about 19 h, about 20 h, about 21 h, about 22 h, about 23 h, about 24 h, a range encompassed by any of the foregoing values, any combination of the foregoing values, or any set of intermediate values encompassed by a range comprising the foregoing values.
- thermoelectric ceramic oxide comprises as a fourth step pressing of the powder from the third step into a pellet at a suitable temperature for a suitable period of time under a suitable pressure.
- the disclosed methods of making a high performance, thermoelectric ceramic oxide comprises as a fourth step pressing of the powder from the third step into a pellet at a temperature of about 298 K to about 373 K for a period of about 1 min to about 30 min at pressure of about 0.1 GPa to about 2 GPa.
- the suitable pressure used in the fourth step is about 0.1 GPa, about 0.2 GPa, about 0.3 GPa, about 0.4 GPa, about 0.5 GPa, about 0.6 GPa, about 0.7 GPa, about 0.8 GPa, about 0.9 GPa, about 1.0 GPa, 1.1 GPa, about 1.2 GPa, about 1.3 GPa, about 1.4 GPa, about 1.5 GPa, about 1.6 GPa, about 1.7 GPa, about 1.8 GPa, about 1.9 GPa, about 2.0 GPa, a range encompassed by any of the foregoing values, any combination of the foregoing values, or any set of intermediate values encompassed by a range comprising the foregoing values.
- the suitable period of time in the fourth step is about 1 min, about 5 min, about 10 min, about 15 min, about 20 min, about 25 min, about 30 min, a range encompassed by any of the foregoing values, any combination of the foregoing values, or any set of intermediate values encompassed by a range comprising the foregoing values.
- the suitable temperature in the fourth step is a temperature from about 290 K to about 380 K. In a still further aspect, the suitable temperature in the fourth step is a temperature from about 291 K to about 379 K. In a yet further aspect the suitable temperature in the fourth step is a temperature from about 292 K to about 378 K. In a still further aspect, the suitable temperature in the fourth step is a temperature from about 293 K to about 377 K. In a yet further aspect, the suitable temperature in the fourth step is a temperature from about 294 K to about 376 K. In a still further aspect, the suitable temperature in the fourth step is a temperature from about 295 K to about 375 K.
- the suitable temperature in the fourth step is a temperature from about 296 K to about 374 K. In a still further aspect, the suitable temperature in the fourth step is a temperature from about 297 K to about 373 K. In a yet further aspect, the suitable temperature in the fourth step is a temperature from about 298 K to about 373 K.
- the suitable temperature in the fourth step is a temperature of about 290 K, about 295 K, about 300 K, about 305 K, about 310 K, about 315 K, about 320 K, about 325 K, about 330 K, about 335 K, about 340 K, about 345 K, about 350 K, about 355 K, about 360 K, about 365 K, about 370 K, about 375 K, a range encompassed by any of the foregoing values, any combination of the foregoing values, or any set of intermediate values encompassed by a range comprising the foregoing values.
- the disclosed methods of making a doped thermoelectric ceramic oxide comprises as a fifth step sintering of the pellets from the fourth step in a suitable heating apparatus in the presence of oxygen at a suitable temperature for a suitable period of time.
- the suitable heating apparatus can be a furnace, such as a tube furnace.
- in the presence of oxygen can be a gas mixture enriched in oxygen or a standard, ambient air mixture.
- the suitable period of time for the fifth step is about 10 min to about 120 h, any value or set of intermediate values encompassed by the foregoing values, or any sub-range within the foregoing values.
- the suitable period of time for sintering can be several days to several weeks.
- the suitable temperature for sintering can be about 1123 K to about 1630 K, any value or set of intermediate values encompassed by the foregoing values, or any sub-range within the foregoing values.
- the present disclosure relates to methods of using the disclosed thermoelectric ceramic oxide compositions in various systems and products in which heat, including both waste heat, intentionally generated heat, or uncaptured heat, in a system is converted to electricity using a solid-state conversion device comprising a disclosed thermoelectric ceramic oxide composition.
- the disclosed solid-state conversion device can further comprise components such as, but not limited to DC-DC inverters, DC regulators, rechargeable batteries, and the like.
- the present disclosure pertains to a method of generating an electrical current, the method comprising a solid-state conversion systems and devices comprising a disclosed thermoelectric ceramic oxide composition.
- thermoelectric ceramic oxide composition in various aspects, disclosed herein are solid-state conversion systems and devices comprising a disclosed thermoelectric ceramic oxide composition. In further various aspects, disclosed herein are solid-state conversion systems and devices comprising a disclosed thermoelectric ceramic oxide composition made by a disclosed method of making the disclosed thermoelectric ceramic oxide compositions.
- a devices and systems comprising a solid-state energy conversion device comprising one or more disclosed thermoelectric ceramic oxide composition to provide electricity from heat generated in the product or system.
- exemplary, but non-limiting examples include a system comprising a solid-state energy conversion device comprising one or more disclosed thermoelectric ceramic oxide composition that utilizes the heat radiation from a steel forming process; a system comprising a solid-state energy conversion device comprising one or more disclosed thermoelectric ceramic oxide composition that utilizes waste heat recovery in an automobile, such as recovery of energy from an exhaust system; a system comprising a solid-state energy conversion device comprising one or more disclosed thermoelectric ceramic oxide composition that utilizes heat radiation from a diesel marine engine; a system comprising a solid-state energy conversion device comprising one or more disclosed thermoelectric ceramic oxide composition that utilizes heat generated in a hypersonic vehicle; a system comprising a solid-state energy conversion device comprising one or more disclosed thermoelectric ceramic oxide composition that utilizes heat energy from a power generation system, e.g.,
- references are cited herein throughout using the format of reference number(s) enclosed by parentheses corresponding to one or more of the following numbered references. For example, citation of references numbers 1 and 2 immediately herein below would be indicated in the present disclosure as (Refs. 1 and 2). These references are incorporated by reference in their entirety.
- a doped thermoelectric ceramic oxide having the following formula: Ca 3-x M 2 x Co 4 O 9 M 1 y ; wherein x is a number having a value from about 0.00 to about 3; wherein y is a number having a value from about 0.01 to about 0.50; wherein M 1 is a first metal dopant comprises a metal selected from group 1 metals, group 2 metals, transtition metals, post-transitional metals, group 14 metals, group 15 metals, group 16 metals, and rare earth elements; and wherein M 2 is a second metal dopant comprising at least one rare earth element.
- Aspect 7 The doped thermoelectric ceramic oxide of any one of 1-Aspect 6, wherein the first metal dopant comprises a metal selected from group 14 metals, group 15 metals, group 16 metals, and rare earth elements.
- Aspect 8 The doped thermoelectric ceramic oxide of any one of 1-Aspect 6, wherein the first metal dopant comprises a metal selected from group 1 metals, group 2 metals, transition metals, and post-transtition metals.
- thermoelectric ceramic oxide of Aspect 9 wherein the first metal dopant comprises a metal selected from Bi and K.
- thermoelectric ceramic oxide of Aspect 10 wherein the first metal dopant comprises Bi.
- thermoelectric ceramic oxide of Aspect 10 wherein the first metal dopant comprises K.
- thermoelectric ceramic oxide of Aspect 13 wherein the second metal dopant comprises a metal selected from Tb, Pr, and combinations thereof.
- thermoelectric ceramic oxide of Aspect 14 wherein the second metal dopant comprises Tb.
- thermoelectric ceramic oxide of Aspect 14 wherein the second metal dopant comprises Pr.
- thermoelectric ceramic oxide of any one of 1-Aspect 16 wherein the first metal dopant comprises a metal selected from Bi, Ba, and K; and wherein the second metal dopant comprises a metal selected from Tb, Pr, and combinations thereof.
- Aspect 18 The doped thermoelectric ceramic oxide of Aspect 17, wherein the first metal dopant comprises Bi; and wherein the second metal dopant comprises a metal selected from Tb, Pr, and combinations thereof.
- Aspect 19 The doped thermoelectric ceramic oxide of Aspect 18, wherein the first metal dopant comprises Bi; and wherein the second metal dopant comprises Tb.
- Aspect 20 The doped thermoelectric ceramic oxide of Aspect 18, wherein the first metal dopant comprises Bi; and wherein the second metal dopant comprises Pr.
- Aspect 21 The doped thermoelectric ceramic oxide of Aspect 17, wherein the first metal dopant comprises Ba; and wherein the second metal dopant comprises a metal selected from Tb, Pr, and combinations thereof.
- Aspect 22 The doped thermoelectric ceramic oxide of Aspect 21, wherein the first metal dopant comprises Ba; and wherein the second metal dopant comprises Tb.
- Aspect 23 The doped thermoelectric ceramic oxide of Aspect 21, wherein the first metal dopant comprises Ba; and wherein the second metal dopant comprises Pr.
- Aspect 24 The doped thermoelectric ceramic oxide of Aspect 17, wherein the first metal dopant comprises K; and wherein the second metal dopant comprises a metal selected from Tb, Pr, and combinations thereof.
- Aspect 25 The doped thermoelectric ceramic oxide of Aspect 24, wherein the first metal dopant comprises K; and wherein the second metal dopant comprises Tb.
- Aspect 26 The doped thermoelectric ceramic oxide of Aspect 24, wherein the first metal dopant comprises K; and wherein the second metal dopant comprises Pr.
- thermoelectric ceramic oxide of any one of 1-Aspect 26 further comprising a plurality of grains comprising intragranular structures, wherein the first metal dopant dopant, the first metal dopant dopant, or both are present in the intragranular structures.
- Aspect 28 The doped thermoelectric ceramic oxide of any one of 1-Aspect 27, further comprising a plurality of grain boundaries disposed between adjacent grains, wherein the first metal dopant is present in the grain boundaries.
- a method of making a doped thermoelectric ceramic oxide comprising: doping a ceramic oxide formulation with a first metal dopant, M 1 , in a sol-gel process resulting in a gel; heating the gel to form an ash; grinding the ash into an ash-based powder; compressing the ash-based powder into a pellet; and sintering the pellet to form the doped thermoelectric ceramic oxide.
- first metal dopant comprises a metal selected from group 1 metals, group 2 metals, group 2 metals, transtition metals, group 14 metals, group 15 metals, group 16 metals, and rare earth elements.
- Aspect 31 The method of Aspect 30, wherein the first metal dopant comprises a metal selected from group 14 metals, group 15 metals, group 16 metals, and rare earth elements.
- Aspect 32 The method of Aspect 30, wherein the first metal dopant comprises a metal selected from group 1 metals, group 2 metals, transition metals, and post-transtition metals.
- Aspect 33 The method of Aspect 30, wherein the first metal dopant comprises a metal selected from K, Bi, Ce, Nb, Yb, Lu, and Ba.
- Aspect 34 The method of Aspect 33, wherein the first metal dopant comprises a metal selected from Bi and K.
- Aspect 35 The method of Aspect 34, wherein the first metal dopant comprises Bi.
- Aspect 36 The method of Aspect 34, wherein the first metal dopant comprises K.
- Aspect 37 The method of any one of Aspect 29-Aspect 36, wherein the doped thermoelectric ceramic oxide has the molecular formula Ca 3 Co 4 O 9+ ⁇ M 1 y , where M 1 is a metal selected from K, Bi, Ce, Nb, Yb, Lu, and Ba, where y is a number having a value from about 0.01 to about 0.50.
- Aspect 38 The method of any one of Aspect 29-Aspect 37, further comprising doping the ceramic oxide formulation with a second metal dopant, M 2 , in the sol-gel process.
- Aspect 39 The method of Aspect 38, wherein the second metal dopant comprises at least one rare earth element.
- Aspect 40 The method of Aspect 39, wherein the second metal dopant comprises a metal selected from La, Ce, Tb, Pr, Nd, Pm, Sm, Eu, Gd, Dy, Ho, Er, Tm Yb, Lu, and combinations thereof.
- Aspect 41 The method of Aspect 40, wherein the second metal dopant comprises a metal selected from Tb, Pr, and combinations thereof.
- Aspect 42 The method of Aspect 41, wherein the second metal dopant comprises Tb.
- Aspect 43 The method of Aspect 41, wherein the second metal dopant comprises Pr.
- Aspect 44 The method of Aspect 39, wherein the first metal dopant comprises Bi; and wherein the second metal dopant comprises a metal selected from Tb, Pr, and combinations thereof.
- Aspect 45 The method of Aspect 44, wherein the first metal dopant comprises Bi; and wherein the second metal dopant comprises Tb.
- Aspect 46 The method of Aspect 44, wherein the first metal dopant comprises Bi; and wherein the second metal dopant comprises Pr.
- Aspect 47 The method of Aspect 39, wherein the first metal dopant comprises Ba; and wherein the second metal dopant comprises a metal selected from Tb, Pr, and combinations thereof.
- Aspect 48 The method of Aspect 47, wherein the first metal dopant comprises Ba; and wherein the second metal dopant comprises Tb.
- Aspect 49 The method of Aspect 47, wherein the first metal dopant comprises Ba; and wherein the second metal dopant comprises Pr.
- Aspect 50 The method of Aspect 39, wherein the first metal dopant comprises K; and wherein the second metal dopant comprises a metal selected from Tb, Pr, and combinations thereof.
- Aspect 51 The method of Aspect 50, wherein the first metal dopant comprises K; and wherein the second metal dopant comprises Tb.
- Aspect 52 The method of Aspect 50, wherein the first metal dopant comprises K; and wherein the second metal dopant comprises Pr.
- Aspect 53 The method of Aspect 38, wherein the doped thermoelectric ceramic oxide has the molecular formula Ca 3-x M 2 x Co 4 O 9 M 1 y , where first metal dopant, M 1 , is a metal selected from Bi, Ce, Nb, Yb, Lu, and Ba; wherein the first metal dopant dopant, M 2 , is a metal selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu, as described herein, x is a number having a value of from about 0.0 to about 3.0, and y is a number having a value of from about 0.01 to about 0.50.
- first metal dopant, M 1 is a metal selected from Bi, Ce, Nb, Yb, Lu, and Ba
- the first metal dopant dopant, M 2 is a metal selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, T
- Aspect 54 The method of Aspect 53, wherein x is a number having a value from about 0.01 to about 3.
- Aspect 55 The method of Aspect 53, wherein x is a number having a value from about 0.00 to about 0.1.
- Aspect 56 The method of Aspect 53, wherein x is a number having a value from about 0.01 to about 0.1.
- a solid-state conversion device comprising a disclosed thermoelectric ceramic oxide composition made by the method of Aspect 29.
- the present work applied conventional cold pressing and sintering to make the oxide pellets using the powders synthesized through the chemical sol-gel route, to precisely control the stoichiometry and dopants distribution with strict uniformity.
- the precursor powders were obtained mixing chemical reagents: Ca(NO 3 ) 2 ⁇ 4H 2 O (99%, Acros Organics), Co(NO 3 ) 2 ⁇ 6H 2 O (99%, Acros Organics), Bi(NO 3 ) 3 ⁇ 5H 2 O (98%, Acros Organics), and Tb(NO 3 ) 3 ⁇ 6H 2 O (99.9% Strem Chemicals) in deionized water according to the stoichiometric chemical compositions.
- the citric acid (BDH Chemical), ethylene glycol, and polyethylene glycol were dissolved in the solution to polymerize the mixture.
- Nitric acid was included in the solution to promote the sol-gel synthesis, nitrate salts decomposition, and the new compound formation.
- the sol-gel mixture was mechanically stirred at 353 K for 3 h.
- the obtained sol-gel mixture was ashed at 773 K for 2 hr in the air inside a box furnace.
- the subsequent ashes were ball-milled in ethyl alcohol in a stage with zirconia balls and then dried at room temperature with a final manually ground stage after that to obtain uniform grain size in the powder.
- the reasonable homogeneous ashes were calcined at 973 K for 4 h in a tube furnace with constant oxygen flow.
- the calcined powders were uniaxially pressed into round pellets under a 1 Gpa pressure at room temperature.
- the bulk samples were sintered at 1233 K in a tube furnace with constant oxygen flow and then cut into rectangular pellets to obtain the final desired sample for either the electrical or thermal measurements.
- the apparent densities for all bulk samples are listed in Table 1.
- C p , ⁇ , and m are the specific heat, thermal diffusivity, and mass density, respectively.
- the Cp and ⁇ values were obtained in the range 323 to 1073 K using a Linseis Laser Flash Analyzer 1200. The measurements were also performed perpendicular to the pressed direction and samples were analyzed under a low-pressure air environment.
- X-Ray powder Diffraction (XRD) analysis was performed using a PANatycal X'Pert Pro XRD unit for crystal phase and lattice parameter determination purposes. The ground powders from the sintered samples were used in the XRD analysis using Cu K-alpha radiation, 45 kV voltage and 40 mA current at room temperature.
- TEM Transmission electron microscopy
- EDS Energy dispersive spectroscopy
- HAADF High-angle annular dark-field
- the conventional chemical sol-gel method was used to synthesize the precursor powders, which were subsequently subjected to calcination followed by pelletization and sintering to formulate the bulk scale pellets, as shown in FIG. 1 .
- Dopants were introduced at the sol-gel state to ensure the strict chemistry and stoichiometry changes in the final bulk ceramics.
- the heavy rare earth element of Tb is first introduced as a dopant to scatter phonons and reduce the thermal conductivity.
- the samples with dual dopants all present much higher Seebeck coefficient than that with Tb doping alone.
- the power factor of Ca 2.95 Tb 0.05 Co 4 O 9 Bi 0.25 at 310 K is 1.83 mWm ⁇ 1 K ⁇ 2 which is by far the highest power factor reported for Ca 3 Co 4 O 9+ ⁇ synthesized with different methods and incorporation with different dopants. (Refs 26, 27).
- the best performing Ca 2.95 Tb 0.05 Co 4 O 9 Bi 0.25 maintains an exceptional high power factor of 1.23 mWm ⁇ 1 K ⁇ 2 .
- the total K is cumulative of the electronic thermal conductivity (K e ) and the lattice thermal conductivity (K i ), as depicted in FIGS. 2 A- 2 F for different Ca 3-x Tb x Co 4 O 9 Bi y .
- Bi doping level there is an increase in a, b 1 , c, and ⁇ , which is accompanied by the decrease in the lattice parameter b 2 .
- Bi addition also triggers major microstructure changes.
- the crystal grain anisotropy is thus increased, implying the faster grain growth and faster diffusion along the a-b plane during the sintering.
- Such an increase in grain anisotropy is also accompanied by the improvement of the crystal texture.
- the crystals have the c-axis of the monoclinic structure more or less parallel to the pressed direction of the pellets for Ca 2.95 Tb 0.05 Co 4 O 9 Bi y ⁇ 0.25 samples, although the misorientation angle ⁇ 30 degrees between the neighboring grains are commonly observed.
- With the increase in the Bi doping level to y 0.3, there is abnormal large grain growth with random orientation.
- TEM transmission electron microscopy
- the atomic structure of the grain boundaries is further revealed by the atomic resolution Z-contrast imaging. Consistent with the TEM EDS results, the Ca 2.95 Tb 0.05 Co 4 O 9 sample did not present any brighter column at the grain boundaries indicating the lack of the heavy element Tb at the grain boundaries. Interestingly, the grain boundaries of Ca 3 Co 4 O 9 Bi 0.25 sample present the bright column exclusively and periodically on the Co sites layer within the electrically insulating rock-salt-type Ca 2 CoO 3 misfit layers. Such brighter atom columns initiated at the GB plane and extend about 3-4 atomic spacing into the grain interior. Such brighter contrast indicating the Bi segregation at the Co sites at the grain boundaries of Ca 3 Co 4 O 9 Bi 0.25 sample.
- Non-stoichiometric doping with dual elements of Tb and Bi does not result in the crystal structure changes or the secondary phase formation. Nevertheless, the dual dopants have resulted in the systematic microstructure evolution, as schematized in FIGS. 6 A- 6 C , including the increased grain anisotropy, improved crystal grain alignment and the segregation of dopants at the grain boundaries. Consistent with our previous results incorporating three different sets of the dopants K + , Ba 2+ , and Bi 3+ (Refs. 30, 31, 32) the present results indicate that the grain boundaries of the Ca 3 Co 4 O 9 ceramics apparently attract oversized dopants and deplete the undersized dopants.
- the segregation of the oversized dopants decreases the grain boundary energy and facilitates fast diffusion along the grain boundaries and crystal texture development. With appropriate doping level, such dopants grain boundary segregation and crystal alignment have profoundly decreased the electrical resistivity and simultaneously increased the Seebeck coefficient.
- the Bi 3+ with larger ionic radius will inevitably increase the abundance of Co 4+ ions with smaller ionic radius than that of Co 3+ ions.
- the Seebeck coefficient thus increased accordingly.
- the dopants segregation at grain boundaries could render the formation of the space-charge layer adjacent to the grain boundary plane and lead to the redistribution of defects and solutes in the grain interiors (Refs. 34, 35) and overwhelmingly affect Seebeck coefficient.
- the carriers with energy higher than the Fermi energy contribute positively to the Seebeck coefficient, while the carriers with energy lower than the Fermi energy contribute negatively.
- the peak ZT of 0.90 is the highest ZT value reported for Ca 3 Co 4 O 9 oxide ceramics, as shown in Table 3 and FIG. 11 .
- the sample of Ca 2.95 Tb 0.05 Co 4 O 9 ⁇ Bi 0.25 is also with the high plateau of ZT 0.35 at 373K and ZT of 0.90 at 1073K, as shown in FIGS. 7 A- 7 E .
- Such high plateau leads to the high average ZT, (Ref. 37) which is very much desired for high-performance TE materials.
- the Ca 2.95 Tb 0.05 Co 4 O 9 ⁇ Bi y sample outperformed the single-crystal Ca 3 Co 4 O 9+ ⁇ (Ref. 13) and Ca 2.9 Bi 0.1 Co 4 O 9 ⁇ (Ref. 35) single crystals, as shown in FIGS. 7 A- 7 E .
- the Ca 2.95 Tb 0.05 Co 4 O 9 ⁇ Bi 0.25 polycrystalline ceramics possess the apparent lower thermal conductivity in comparison with that of the single crystals.
- the Ca 2.95 Tb 0.05 Co 4 O 9 ⁇ Bi y polycrystalline also possess the higher electrical power factor than that of the single crystals, especially at the low-temperature regime.
- Such power factor Ca 2.95 Tb 0.05 Co 4 O 9 ⁇ Bi y polycrystalline ceramics have directly resulted from the higher electrical Seebeck coefficient and low resistivity.
- the Ca 2.95 Tb 0.05 Co 4 O 9 ⁇ Bi 0.25 polycrystalline ceramics possess the high abundance of grain boundaries with the misorientation angle of ⁇ 30°.
- the low resistivity in Ca 2.95 Tb 0.05 Co 4 O 9 ⁇ Bi 0.25 comparable to that of the single crystals immediately reveals that, when incorporating with dopants segregation the grain boundaries with the misorientation angle of ⁇ 30°, the grain boundaries are not deteriorating the electrical conductivity.
- Such results are very encouraging for practical application in the production of TE using polycrystalline oxide ceramics.
- thermoelectric materials the creation of the grain boundaries and interfaces through the nanostructure engineering is to suppress the thermal conductivities.
- the electrical conductivity is heavily affected by the grain boundaries, while the Seebeck coefficient is not affected by the grain boundary properties.
- the grain size and grain boundary density could be tuned by changing the sintering temperature.
- the thermal conductivities and electrical conductivities both increase with the increase of the grain size, the Seebeck coefficient keeps unchanged for the samples with different grain size. (Refs. 39, 40, 41).
- the impact of the grain boundary on the Seebeck coefficient changes when there are dopants segregated to the grain boundaries.
- dopants segregation remains sharply at the GB plane, without forming the amorphous or crystal secondary phase, thus eliminating the excessive scattering of the carrier and avoiding the increase in electrical resistivity.
- the dopants segregation provides a barrier and filter the low energy carrier thus further decrease the carrier concentration and increase the Seebeck coefficient. In other words, when the dopants segregation is two dimensional, it cannot be simply analog to the impurity scattering.
- the high ZT from Ca 2.95 Tb 0.05 Co 4 O 9 ⁇ Bi y is achieved by using only two dopants.
- the designed chemistry is tunable in term of dopant species and doping level.
- the sample Ca 2.94 Pr 0.03 Tb 0.03 Co 4 O 9 Bi 0.23 is with comparable ZT to that of Ca 2.95 Tb 0.05 Co 4 O 9 ⁇ Bi 0.25 .
- the ZT in polycrystalline ceramics could be further improved by lowering the thermal conductivity using the nano-inclusions as those developed for SiGe, Bi 2 Te 3 , and Si (Ref. 42) systems.
- non-stoichiometric dopants addition dramatic increased the electrical conductivity and Seebeck coefficient and resulting in the polycrystalline oxide ceramics outperforming single crystals in a wide temperature range.
- Heavy element Bi non-stoichiometric addition and the resultant the Bi substation in both the Ca and Co site within the unit cell suggested the versatility of designing the layered oxide with nano-blocks.
- Dual dopants resulted in systematic microstructure evolution, including the increased grain anisotropy, improved crystal grain alignment and the segregation of dopants at the grain boundaries.
- the oxide Ca 3 Co 4 O 9 ⁇ crystal texture and GB density can be both controlled by intragranular doping and especially the appropriate dopants GB segregation or depletion.
- the dopants segregating at the GBs promote the crystal texture and facilitate the large carrier mobility and high electrical conductivity, the dopants GB segregation will act as carrier filter to decrease the carrier concentration and simultaneously increase the Seebeck coefficient.
- the grain boundaries with the misorientation angle of 30° are not deteriorating the electrical conductivity, resulting in the electrical conductivity of polycrystalline ceramics comparable to that of the single crystals.
- the present work shed light about the new direction for engineering the atomic structure of grain boundaries to dramatically improve the performance of various TE materials.
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Abstract
Description
ZT=S 2 σT/K
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κ=λC pμm
TABLE 1 |
Apparent density of the Ca3-xTbxCo4O9Biy samples. |
Ca3-xTbxCo4O9Biy | Average Apparent density (g/cm3) | |
x = 0 y = 0 | 3.883 | |
x = 0.05 y = 0 | 4.182 | |
x = 0.30 y = 0 | 4.477 | |
x = 0.50 y = 0 | 4.571 | |
x = 0.05 y = 0.10 | 3.911 | |
x = 0.05 y = 0.15 | 3.909 | |
x = 0.05 y = 0.20 | 3.970 | |
x = 0.05 y = 0.25 | 4.295 | |
x = 0.05 y = 0.30 | 4.701 | |
TABLE 2 |
Lattice parameters a, b1, b2, c, and β for the single doped |
Ca3-xTbxCo4O9 (x = 0, and 0.05) and the dual doped |
Ca2.95Tb0.05Co4O9Biy (y = 0.10, 0.15, 0.20, 0.25, and 0.30) |
samples. b1 and b2 refer to b-axis lattice parameters in the |
rock-salt layer Ca2CoO3 and the CoO2 layer, respectively. |
Ca3-xTbxCo4O9Biy | a (Å) | b1 (Å) | b2 (Å) | c (Å) | β (°) |
x = 0; y = 0 | 4.859 | 4.562 | 2.747 | 10.849 | 98.711 |
x = 0.05; y = 0 | 4.858 | 4.552 | 2.749 | 10.847 | 98.697 |
x = 0.05; y = 0.10 | 4.878 | 4.573 | 2.744 | 10.879 | 99.052 |
x = 0.05; y = 0.15 | 4.880 | 4.571 | 2.743 | 10.876 | 98.955 |
x = 0.05; y = 0.20 | 4.880 | 4.566 | 2.743 | 10.880 | 99.038 |
x = 0.05; y = 0.25 | 4.915 | 4.562 | 2.738 | 10.926 | 99.725 |
x = 0.05; y = 0.30 | 4.848 | 4.548 | 2.752 | 10.862 | 98.377 |
TABLE 3 |
Progression of the performance of Ca3Co4O9 thermoelectric material. |
S | ρ | κ | |||
Ref | Year | Stoichiometry | (μV/K) | (μΩm) | (W/Km) |
(13) | 2000 | Ca2.5Bi0.5Co4O9 | 160 | 95 | 1.37 |
(61) | 2002 | Ca2.4Bi0.3Na0.3Co4O9 | 204 | 75 | 1.75 |
(14) | 2003 | Ca3Co4O9 single crystal | 245 | 23 | 2.90 |
(53) | 2004 | Ca2.7Eu0.3Co4O9 | 194 | 78 | 1.65 |
(62) | 2004 | Ca2.7Dy0.3Co4O9 | 190 | 85 | 1.60 |
(63) | 2005 | Ca3Co4O9/Ag-10 wt % | 175 | 30 | |
(24) | 2006 | Ca2.9Bi0.1Co4O9 | 200 | 14.5 | 3.00 |
single crystal | |||||
(64) | 2008 | Ca2.7Ag0.3Co4O9 | 229 | 75 | 2.10 |
(54) | 2008 | Ca2.7Gd0.3Co4O9 | 182 | 78 | 1.40 |
(55) | 2009 | Ca2.7Ag0.3Co4O9/ | 218 | 37 | 2.50 |
Ag-10 wt % | |||||
(65) | 2009 | Ca2.7Y0.3Co4O9 | 172 | 85 | 1.55 |
(56) | 2010 | Ca3Co3.7Ti0.3O9 | 285 | 165 | 1.80 |
(66) | 2010 | Ca3Co3.9Fe0.1O9 | 258 | 97 | 1.78 |
(67) | 2010 | Ca3Co3.95Ga0.05Co9 | 200 | 77 | 1.50 |
(68) | 2011 | Ca2.97Ag0.03Co4O9 | 200 | 89 | 2.10 |
(69) | 2011 | Ca2.7Er0.3Co4O9 | 192 | 100 | 1.42 |
(70) | 2011 | Ca2.8Lu0.2Co4O9 | 194 | 95 | 1.20 |
(57) | 2011 | Ca2.8Ag0.05Lu0.15Co4O9 | 235 | 72 | 1.40 |
(71) | 2011 | Ca2.8Pr0.2Co4O9 | 201 | 107 | 1.55 |
(72) | 2014 | Ca3Co3.85Cr0.15O9 | 195 | 110 | 2.00 |
(58) | 2014 | Ca2.7Bi0.3Co3.9Fe0.1O9 | 182 | 73 | 1.19 |
(73) | 2014 | Ca2.9La0.1Co3.9Fe0.1O9 | 226 | 125 | 1.29 |
(74) | 2014 | Ca3Co3.9Cd0.1O9 | 209 | 82 | 1.50 |
(75) | 2015 | Ca3Co4O9 | 132 | 184 | 0.41 |
(33) | 2015 | Ca3Ba0.05Co4O9 | 185 | 41 | 1.70 |
(76) | 2016 | Ca2.8Ba0.1Pr0.1Co4O9 | 207 | 92 | 1.65 |
(77) | 2016 | Ca3Co4O9 + | 230 | 125 | 1.32 |
5 wt. % K2CO3 | |||||
(25) | 2016 | Ca2.8Bi0.2Co4O9 | 192 | 50 | 1.90 |
(78) | 2016 | Ca3Co4O9 | 170 | 175 | 0.49 |
(79) | 2017 | Ca2.55Na0.45Co4O8.55F0.45 | 192 | 130 | 2.20 |
(59) | 2017 | Ca3Co4O9 | 210 | 171 | 0.63 |
(80) | 2017 | Ca2.9Bi0.1Ba0.07Co4O9 | 190 | 40 | |
(32) | 2018 | Ca3Co4O9K0.1 | 190 | 44 | |
(81) | 2018 | Ca2.95Na0.05Co3.975W0.025O9 | 183 | 130 | 1.26 |
(46) | 2018 | Ca3Co4O9 | 189 | 72 | 1.95 |
(60) | 2019 | Ca2.25Na0.3Bi0.35Tb0.1Co4O9 | 236 | 86 | 1.96 |
(82) | 2019 | Ca2.97Sr0.03Co4O9 | 275 | 65 | 4.40 |
(83) | 2019 | Ca2.25Na0.3Bi0.35Tb0.1Co4O9 | 240 | 70 | |
* | 2019 | Ca2.95Tb0.05Co4O9Bi0.25 | 212 | 36 | 1.52 |
S2/ρ | T | ||||
Ref | Year | Stoichiometry | (mW/K2m) | ZT | (K) |
(13) | 2000 | Ca2.5Bi0.5Co4O9 | 0.27 | 0.2 | 973 |
(61) | 2002 | Ca2.4Bi0.3Na0.3Co4O9 | 0.55 | 0.32 | 1000 |
(14) | 2003 | Ca3Co4O9 single crystal | 2.61 | 0.87 | 973 |
(53) | 2004 | Ca2.7Eu0.3Co4O9 | 0.48 | 0.30 | 1000 |
(62) | 2004 | Ca2.7Dy0.3Co4O9 | 0.42 | 0.27 | 1000 |
(63) | 2005 | Ca3Co4O9/Ag-10 wt % | 1.02 | 1073 | |
(24) | 2006 | Ca2.9Bi0.1Co4O9 | 2.76 | 0.89 | 973 |
single crystal | |||||
(64) | 2008 | Ca2.7Ag0.3Co4O9 | 0.70 | 0.32 | 1000 |
(54) | 2008 | Ca2.7Gd0.3Co4O9 | 0.42 | 0.24 | 973 |
(55) | 2009 | Ca2.7Ag0.3Co4O9/ | 1.28 | 0.50 | 1000 |
Ag-10 wt % | |||||
(65) | 2009 | Ca2.7Y0.3Co4O9 | 0.35 | 0.22 | 973 |
(56) | 2010 | Ca3Co3.7Ti0.3O9 | 0.49 | 0.29 | 1000 |
(66) | 2010 | Ca3Co3.9Fe0.1O9 | 0.69 | 0.39 | 1000 |
(67) | 2010 | Ca2Co3.95Ga0.05Co9 | 0.52 | 0.36 | 1073 |
(68) | 2011 | Ca2.97Ag0.03Co4O9 | 0.45 | 0.23 | 973 |
(69) | 2011 | Ca2.7Er0.3Co4O9 | 0.37 | 0.28 | 1073 |
(70) | 2011 | Ca2.8Lu0.2Co4O9 | 0.40 | 0.36 | 1073 |
(57) | 2011 | Ca2.8Ag0.05Lu0.15Co4O9 | 0.77 | 0.61 | 1118 |
(71) | 2011 | Ca2.8Pr0.2Co4O9 | 0.38 | 0.24 | 973 |
(72) | 2014 | Ca3Co3.85Cr0.15O9 | 0.35 | 0.19 | 1073 |
(58) | 2014 | Ca2.7Bi0.3Co3.9Fe0.1O9 | 0.45 | 0.37 | 973 |
(73) | 2014 | Ca2.9La0.1Co3.9Fe0.1O9 | 0.41 | 0.32 | 1000 |
(74) | 2014 | Ca3Co3.9Cd0.1O9 | 0.53 | 0.35 | 1000 |
(75) | 2015 | Ca3Co4O9 | 0.12 | 0.29 | 1000 |
(33) | 2015 | Ca3Ba0.05Co4O9 | 0.83 | 0.52 | 1073 |
(76) | 2016 | Ca2.8Ba0.1Pr0.1Co4O9 | 0.47 | 0.31 | 973 |
(77) | 2016 | Ca3Co4O9 + | 0.42 | 0.35 | 1073 |
5 wt. % K2CO3 | |||||
(25) | 2016 | Ca2.8Bi0.2Co4O9 | 0.74 | 0.43 | 1073 |
(78) | 2016 | Ca3Co4O9 | 0.17 | 0.31 | 900 |
(79) | 2017 | Ca2.55Na0.45Co4O8.55F0.45 | 0.28 | 0.13 | 873 |
(59) | 2017 | Ca3Co4O9 | 0.26 | 0.40 | 1073 |
(80) | 2017 | Ca2.9Bi0.1Ba0.07Co4O9 | 0.90 | 1073 | |
(32) | 2018 | Ca3Co4O9K0.1 | 0.82 | 1073 | |
(81) | 2018 | Ca2.95Na0.05Co3.975W0.025O9 | 0.26 | 0.21 | 1000 |
(46) | 2018 | Ca3Co4O9 | 0.50 | 0.28 | 1073 |
(60) | 2019 | Ca2.25Na0.3Bi0.35Tb0.1Co4O9 | 0.65 | 0.35 | 1073 |
(82) | 2019 | Ca2.97Sr0.03Co4O9 | 1.16 | 0.29 | 1073 |
(83) | 2019 | Ca2.25Na0.3Bi0.35Tb0.1Co4O9 | 0.82 | 1073 | |
* | 2019 | Ca2.95Tb0.05Co4O9Bi0.25 | 1.25 | 0.89 | 1073 |
Claims (20)
Ca3-xM2 xCo4O9M1 y
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